Textile and other materials



Patented July 2, 1940 TEXTILE AND OTHER. MATERIALS I Ienry Dreyfus,London, England No Drawing. Application May 5, ---No. 140,897. In GreatBritain May 10 Claims.

This invention relates to textile and other products containing titaniumdioxide and to an improved form of titanium dioxide particularlysuitable for incorporation in artificial silks and 5 other artificialproducts, for example films, moulded objects and the like.

Artificial silk having a low lustre is extensively manufactured with theaid of titanium dioxide. A small proportion of this material is incorlporated in the spinning solution from which the artificial silk isformed. Another method of producing an artificial silk of low lustre isto incorporate titanium dioxide or hydrated titanium dioxide in thealready spun artificial silk, e. g. by 1 interaction of suitablereagents on the material,

or by treating the material with an aqueous dispersion of titaniumdioxide. however, that when artificial silks containing titanium dioxideare coloured the colourations are U in general not so fast to light asthose yielded by the same dyestufis upon similar materials free fromtitanium dioxide. This lack of fastness'to light is particularlynoticeable while the material is wet. Further, artificial silkcontaining 2! titanium dioxide frequently loses strength much morerapidly when exposed to light than similar artificial silk free fromtitanium dioxide.

According to the present invention these undesirable effects of titaniumdioxide are minimized 30 by associating or treating it with a compoundof manganese, iron, cobalt, nickel or copper. These elements are thosehaving atomic weights ranging from that of manganese to that of copper.The titanium dioxide may be treated with the 35 metal compound or amixture of the metal compounds before the titanium dioxide isincorporated in the artificial silk or other material. Again, theartificial silk or other material containing the titanium dioxide may betreated 40 with the metal compound or a mixture of the metal compoundsand either before, during, or after any colouring of the material.

If desired, the treatment of a textile or other product with the metalcompound may precede 45 or be carried out simultaneously with theincorporation of titanium dioxide in the material or as a step in aprocess of effecting such incorporation. Moreover,,a cellulose ester orother substance may be treated with the metal compound 50 prior toconversion into filaments, e. g. while in the form of a spinning orfilm-forming solution,

and before or after, incorporation of titanium dioxide therewith.

Conveniently water-soluble compounds of the 55 metals are employed andthey maybe salts of It has been found,

1937, Serial 14, 1936 the metals with acids or they may be compounds inwhichthe metal forms part of an anion. Examples of suitable salts arethe sulphates, chlorides, or acetates of the aforementioned metals. Thetreatment or association of the titanium dioxide with the metal compoundis applicable in the case of natural textile fibres containing titaniumdioxide, for example natural silk, in which titanium dioxide has beenincorporated. It is, however, of special value in the case of artificialsilk and other artificial products containing titanium dioxide. Forexample, the new process may be applied in the case of regeneratedcellulose artificial silk, foils, or films containing titanium dioxide,or artificial silk, films, foils,

plastics and the like containing titanium dioxide and having a basis ofcellulose acetate or other cellulose ester or ether.

The titanium dioxide or material containing it may be treated with anaqueous solution containing one or more of the aforementioned compounds.For example, titanium dioxide sufliciently finely sub-divided to renderit suitable for incorporation in an artificial silk spinning solutionmay be heated or boiled with a 0.1 to 5%, e. g. 0.3 to 0.5%,aqueoussolution of copper sulphate or other of the metal compounds referred toabove. Again, a textile material, for example an artificial silkcontaining titanium dioxide, may be heated with a dilute aqueoussolution of copper sulphate or other of the above-mentioned metalcompounds. Such a solution may, for example contain .05 to 1% of thecopper sulphate or other compound.

If desired the solutions of the metal compounds may contain an acid, forexample formic acid, acetic acid, or other organic acid. The amount ofacid used may be about half the weight of the metal salt.

When treating textile materials, foils, or the like containing titaniumdioxide, the treatment liquid may contain a swelling agent for thecellulose acetate or other material forming the basis of the textile,foil or the like, in order to facilitate penetration of the material bythe treatment liquid.

After treatment with the aqueous solution the titanium dioxide ormaterial containing it may be washed. The material may then be dried,'orfurther processed without drying, as may be convenient. For example, inthe case of a textile material containing titanium dioxide, the wetmaterial maybe dyed without intermediate drying.

If desired the titanium dioxide or other material may be subjected to atreatment to ensure Y theflxation of an oxide, hydroxide, or other wa-'ter insoluble compound of the metal in the materiaL, For examplesuitable reagents may be allowed to interactin the presence of thetitanium dioxide so as to form an oxide or hydroxide 0f the metal on thetitanium dioxide. For instance finely divided titanium dioxide may beheated with an aqueous solution of a salt oi. one

of the aforementioned metals and an aqueous solution of an alkali slowlyadded in sumcient quantity to precipitate an oxide or hydroxide of themetal on the titanium dioxide.

Other methods of associating with-the titanium dioxide a compound orcompounds of the manganese or other metal may, howevenbe employed. Forexample the titanium dioxide may merely be intimately mixed with thecompound of the metal in question. For instance an aqueous paste oftitanium dioxide may be well ground with an aqueous paste of an oxide orhydroxide of the manganese, copper or other metal, the mixture beingthereafter dried if desired.

The compound of manganese, copper or other metal may be employed inquite small proportion, for example a proportion of the order of .05 to5%, e. g. .5 to 2%, based on the weight of the titanium dioxide.

The new process enables improved results as regards fastness to light tobe obtained when materials containing titanium dioxide are coloured withdyestuffs of widely varying type. For example the improvement isparticularly good in Y the case of water-soluble azo dyestufls having a85 substantive aflinity for regenerated cellulose. Again, the dyestufismay be azo dyes, soluble or insoluble in water, having a direct aillnityfor cellulose acetate. Other classes of dyes the colourations "of whichon textile materials contain- 'ing titanium dioxide may be improved bythe new process are the amino-anthraquinone dyestuffs having directafilnity for cellulose acetate, especially those dyestuffs yieldingviolet, blue or green shades on this material. The improvement isparticularly good in the case of dyeings made with1.4-diamino-anthraquinone or L-i-amino-oxyanthraquinone and theirsubstitution products, for example 1.4-di-(alkylamino) -anthraqulnone.'An improvement may be obtained even in the case of those dyestuffsnormally regarded as having a very high degree of fastness, for examplevat dyestuffs, e. g. those of the indigoid series,

and the water-insoluble azo dyestufl's produced on the fibre, forexample those produced by coupling diazotised amines with p-naphthol,arylamides of 2:3-oxy-naphthoic acid, or diacyl-acetyl derivatives ofaromatic diamines.

The following examples illustrate the invention but are not to beregarded as limiting it in any way:

Example 1 Finely divided titanium dioxide is heated for 30 minutes at 85to 90 C. with 20 times its weight of an aqueous solution containing 4grams per litre of copper sulphate and 1.5 grams per litre of formicacid. The titanium dioxide is then filtered oil, washed and dried.

For the production of artificial silk 0! low lustre 2 parts of titaniumdioxide treated as above are incorporated in 400 parts of a 25% solutionof cellulose acetate in acetone and the solution thereafter spun intofilaments by dry spinning 'methods. Shades yielded on this artificialsilk 7| with, for example, 1.4-di-(methylamino)-anthra-' treatedtitanium dioxide,

The copper sulphate in this example may be replaced by an equalvquantity of manganese 5 sulphate (MnSO4) cobaltssulphate or nickelsulphate.

Example? A fabric of cellulose acetate yarns having a 10 low lustre dueto the presence of titanium dioxide therein is treated for one hour atC. with an aqueous solution containing .5% or copper sulphate and .2% ctformic acid. The material is well washed and is then dyed with 1.4-di-(methw ylamiriohanthraquinone. In this way a blue shade is obtainedwhich is much faster to light than that obtained when the treatment withcopper sulphate is omitted. j

The copper sulphate in this example may be 20 replaced by an equalquantity of nickel sulphate or cobalt sulphate or manganese sulphate(M31304).

Having described my invention, what I desire to secure by Letters Patentis: 25

1. Process for improving the light-fastness 0t colored artificialtextile materials containing titanium dioxide, which comprisesassociating the titanium dioxide with a compound of a metal selectedfrom the group consisting of manganese, 30 iron, cobalt, nickel andcopper, and incorporating the titanium dioxide product so produced intothe art ficial textile materials.

2. Process for improving the light-fastness of colored artificialtextile materials having a basis 35 of cellulose acetate and containingtitanium dioxide, which comprises associating the titanium dioxide witha compound of a metal selected from the group consisting of manganese,iron, cobalt, nickel and copper, and incorporating the 40 titaniumdioxide product so produced into the artificial textile materials havinga basis 01 cellulose acetate. 7

3. Process for improving the light-fastness of colored artificialtextfle materials having a basis 45 of cellulose acetate and containingtitanium dioxide, which comprises associating the titanium dioxide witha compound of a metal selected from the group consisting of manganese,iron, cobalt, nickel and copper, the proportion of such metal socompound being from 0.05 to 1% on the weightof the titanium dioxide, andincorporating the titanium dioxide product so produced into theartificial textile materials having a basis of cellulose acetate. 55

4. Process for improving the light-fastness of colored artificialtextile materials containing titanium dioxide, which comprisessubjecting the artificial materials containing titanium dioxide to theaction of an aqueous medium containing a 60 compound of a metal selectedfrom the group consisting of manganese, iron, cobalt, nickel and copper.

5. Process for improving the light-fastness of colored artificialtextile materials having a basis 05 of cellulose acetate and containingtitanium dioxide, which comprises subjecting artificial textilematerials having a basis of cellulose acetate and containing titaniumdioxide to the action of an aqueous mediumcontaining a compound of a 7metal selected 'from the group consisting of manganese, iron, cobalt,nickel and copper, and. a swelling agent for the cellulose acetate.

6. Process for improving the light-fastness or colored artificialtextile materials having a basis 76 of cellulose acetate and containingtitanium dioxide, which comprises subjecting artificial textilematerials having a basis of cellulose acetate and containing titaniumdioxide to the action of an aqueous medium containing a compound of ametal selected from the group consisting of manganese, iron, cobalt,nickel and copper, in an amount equal to from 0.05 to 1% on the weightof the titanium dioxide, and a swelling agent for the cellulose acetate.

7. Process for improving the light-fastness of colored artificialtextile materials having a basis of cellulose acetate and containingtitanium dioxide, which comprises associating the titanium dioxide withcopper sulphate, and incorporating the titanium dioxide product soproduced into the artificial textile materials having a basis ofcellulose acetate.

8. Process for improving the light-fastness of oxide, which comprisesassociating the titanium dioxide with manganese acetate, andincorporating the titanium dioxide product so produced into theartificial textile materials having a basis of cellulose acetate.

9. Process for improving the light-fastness of colored artificialtextile materials having a basis of cellulose acetate and containingtitanium dioxide, which comprises subjecting artificial textilematerials having a basis of cellulose acetate and containing titaniumdioxide to the action of an aqueous medium containing copper sulphateand a swelling agent for the cellulose acetate.

10. Process for improving the light-iastness of colored artificialtextile materials having a basis of cellulose acetate and containingtitanium dioxide, which comprises subjecting artificial textilematerials having a basis of cellulose acetate and containing titaniumdioxide tothe action of an aqueous medium containing manganese acetateand a swelling agent for the cellulose acetate. 20

HENRY DREYFUS

